Method of dispersing an insoluble material in an aqueous solution and an agricultural formulation

ABSTRACT

A novel agricultural formulation includes at least one finely solid water-insoluble material and at least one novel dispersant containing a polymer synthesized from first and second comonomers. The first comonomer is an α,β-unsaturated oxyacid or anhydride, and the second comonomer is an olefin having at least one polymerizable double bond. Also disclosed is a method for dispersing a finely divided solid insoluble material, in particular, an active water-insoluble agrochemical principal, in an aqueous solution; a method for treating a substrate with such a material or principal; and a method of making an agrochemical formulation, where the methods are based on application of the novel dispersant to the preparation of aqueous dispersions of the solid material and agrochemical principal.

The present invention relates generally to dispersants, for use inagricultural applications, in particular the present invention relatesto methods for the dispersion of insoluble material with copolymericdispersants which dispersions are formed with improved dispersibilityand show improved suspensibility. The present invention also relates tomethods of producing dispersible formulations, the formulations per seand methods of treating substrates with dispersions produced from suchformulations.

The active principles in many agricultural applications are largelyhydrophobic or water insoluble in character and are, by necessity, oftenadministered as finely divided solids suspended in aqueous media. Themajority of these active principles are manufactured and marketed inconcentrated form, possibly with the addition of other insoluble inertfillers, which are then diluted prior to application. For example, theactive principle is typically available in the form of a suspensionconcentrate (SC), wettable powder (WP) or water dispersible granule(WG). However, due to the generally hydrophobic nature of the activeprinciple, the addition of a suitable dispersant is essential in orderto achieve an homogenous dispersion with a minimum of mixing, such asmay be achieved readily by hand or with minimal mechanical mixing.Furthermore, once an homogenous dispersion is achieved, the resultingsuspension must remain stable for a time sufficient, at least, to allowapplication by usual means such as spraying. Any settling, agglomerationor flocculation of the finely divided solid may lead to inconsistent andineffective application as well as blockage of the spraying equipment.It is therefore necessary to provide a dispersant which provides easyand homogenous dispersion and results in a suspension which maintainsits stability during the application of the aqueous dispersion.

Effective dispersants for use in these applications ideally provide asuspension with acceptable dispersibility, suspensibility and lack ofagglomeration. The Collaborative International Pesticides AnalyticalCouncil (CIPAC Handbook Volume 1) defines methods that can be used fordetermining acceptable suspensibility (MT 15.1) and degree ofagglomeration (MT 59.3). For example, in suspension concentratesso-called SC formulations, this can be achieved by the addition of about3-5 w/w % of a standard dispersant. Wettable powder (WP) and waterdispersible granule (WG) formulations generally require the addition ofstandard dispersant in the order of 6-7 w/w % in order to achieveacceptable suspensibility and degree of agglomeration as determined by awet sieve retention test. (MT 59.3).

Currently used dispersants for SC formulations include ethyleneoxide/propylene oxide block copolymer surfactants based on anhydrophobic moiety plus ethyleneoxide. Also used are ether phosphatederivatives of non-ionic surfactants, especially of tristyrylphenolethoxylates. Conventional anionic surfactants used include sulphonatedderivatives of arylformaldehyde condensates, polyacrylates andlignosulfonates.

Dispersants for WP and WG formulations are usually limited by therequirement that the dispersant be solid at ambient temperatures, benon-gelling and not dissolve the active principle. For these reasons,conventional non-ionic surfactants are often unsuitable, and anionicdispersants are preferred. Known effective dispersants for WP and WGformulations include sulphonated alkylnaphthalene/formaldehydecondensate salts and lignosulfonate salts.

α-Olefin-polycarboxylate copolymers are well known as dispersants in awide range of applications including pigment dispersion, emulsionpolymerisation, cosmetics and pesticidal compositions. As far back as1972 the sodium salt of a maleic anhydride and diisobutylene copolymerwas given an exemption from tolerance for use in pesticide formulationsby the United States Environmental Protection Authority following apetition from Rohm and Haas Co. FR 2545325 describes the use of ammoniumand alkali metal salts of maleic anhydride-diisobutylene copolymer inpesticide granules. Similarly, EP 201417 describes the use of copolymersof maleic anhydride with surfactants selected from sulfates andphosphates of ethoxylated phenol derivatives in WP and WG formulations.JP 62036303 describes copolymers having a molecular weight range of from5000-20000 for use with granular agrochemical compositions. Maleicanhydride and diisobutylene copolymer derivatives are described for usein conjunction with CaCO₃ and Mg salts for SC formulations in JP 0609,302. The use of sulfonated derivatives of copolymers of maleicanhydride in water dispersable granules is also described in JP58-131903.

French Patent No. 2,397,444 describes stable and concentrateddispersions of active materials which may be prepared from non-dustingpowders or granular materials. It is necessary to separate the activematerial in the presence of a salt of an acidic resin, such as, forexample, a copolymer of maleic anhydride and an α-olefinic compound; addan organic solvent which forms, together with the aqueous medium, atwo-phase system; treat such two-phase system by adding a carriersubstance thereto; and then isolate the product by a reduction in thevolume of the organic phase by the addition of water, the solventgradually transferring into the added water.

We have now found that the use of certain of a range of derivatisedcopolymers comprising olefin monomers and α,β-unsaturated oxyacidmonomers surprisingly provides improvements in dispersibility of WGformulations and suspensibility of dispersed agricultural activeingredients when compared to use of the parent copolymer. Theimprovement is also found surprisingly not only in alternatingcopolymers but in a range of other copolymers including random and blockcopolymers.

We have found that agriculturally acceptable salts or other watersoluble derivatives of alternating copolymers for use as dispersants inagricultural compositions provide improved and consistent dispersantperformance when compared to conventionally used dispersants such assulphonated alkylnaphthalene formaldehyde condensate salts. However, wehave found further derivatisation not only of these copolymers but ofnon-alternating copolymers provides even greater improvement.

Methods for making such copolymers and derivatizations herein describedwill be well known to those skilled in the art of polymer synthesis.

According to a first aspect of the present invention, there is provideda method of dispersing an insoluble material in an aqueous solutioncomprising the following steps:

-   -   (i) providing a formulation comprising at least one insoluble        material and at least one dispersant comprising a copolymer        wherein said copolymer comprises a residue of a first comonomer        and a residue of a second comonomer, wherein said first        comonomer is an α,β-unsaturated oxyacid or anhydride and said        second comonomer is an olefin having at least one polymerizable        double bond and wherein at least one of said first comonomer and        said second comonomer is substituted, wherein the substituents        for said first comonomer are selected from the group consisting        of esters, amides, thioesters and functional groups derived from        reaction with nucleophilic reagents and wherein the substituents        for the second comonomer are selected from the group consisting        of epoxides; sulfonates; esters; amides; and optionally        substituted pendent aromatic and heteroaromatic groups wherein        said optional substituents are selected from the group        consisting of sulfonates, nitrates, phosphates and other        substituents derived from reaction with electrophilic reagents.    -   (ii) dispersing said formulation in an aqueous medium.

According to a second aspect of the present invention, there is provideda method of making an agrochemical formulation comprising the steps of:

-   -   (i) combining at least one insoluble material, and at least one        dispersant comprising a copolymer wherein said copolymer        comprises a residue of a first comonomer and a residue of a        second comonomer, wherein said first comonomer is an        α,β-unsaturated oxyacid or anhydride and said second comonomer        is an olefin having at least one polymerizable double bond and        wherein at least one of said first comonomer and said second        comonomer is substituted, wherein the substituents for said        first comonomer are selected from the group consisting of        esters, amides, thioesters and other functional groups derived        from reaction with nucleophilic reagents and wherein the        substituents for the second comonomer are selected from the        group consisting of epoxides; sulfonates; esters; amides; and        optionally substituted pendent aromatic and heteroaromatic        groups wherein said optional substituents are selected from the        group consisting of sulfonates, nitrates, phosphates and other        substituents derived from reaction with electrophilic reagents;    -   (ii) milling said combination to a particle size range in order        to obtain a stable, readily-suspendible aqueous dispersion; and    -   (iii) stabilising said aqueous dispersion to obtain an SC        formulation suitable for dilution in water for agricultural use.

According to a third aspect of the present invention, there is provideda method of making an agrochemical formulation comprising the steps of:

-   -   (i) combining at least one insoluble material, with at least one        dispersant comprising a copolymer wherein said copolymer        comprises a residue of a first comonomer and a residue of a        second comonomer, wherein said first comonomer is an        α,β-unsaturated oxyacid or anhydride and said second comonomer        is an olefin having at least one polymerizable double bond and        wherein at least one of said first comonomer and said second        comonomer is substituted, wherein the substituents for said        first comonomer are selected from the group consisting of        esters, amides, thioesters and other functional groups derived        from reaction with nucleophilic reagents and wherein the        substituents for the second comonomer are selected from the        group consisting of epoxides; sulfonates; esters; amides; and        optionally substituted pendent aromatic and heteroaromatic        groups wherein said optional substituents are selected from the        group consisting of sulfonates, nitrates, phosphates and other        substituents derived from reaction with electrophilic reagents;        and    -   (ii) milling said combination to a desired particle size to        obtain a homogeneous wettable powder (WP) formulation.

According to a fourth aspect of the present invention, there is provideda method of making an agrochemical formulation comprising the steps of:

-   -   (i) combining at least one insoluble material suitable for        agricultural use with at least one dispersant comprising a        copolymer wherein said copolymer comprises a residue of a first        comonomer and a residue of a second comonomer, wherein said        first comonomer is an α,β-unsaturated oxyacid or anhydride and        said second comonomer is an olefin having at least one        polymerizable double bond and wherein at least one of said first        comonomer and said second comonomer is substituted, wherein the        substituents for said first comonomer are selected from the        group consisting of esters, amides, thioesters and other        functional groups derived from reaction with nucleophilic        reagents and wherein the substituents for the second comonomer        are selected from the group consisting of epoxides; sulfonates;        esters; amides; and optionally substituted pendent aromatic and        heteroaromatic groups wherein said optional substituents are        selected from the group consisting of sulfonates, nitrates,        phosphates and other substituents derived from reaction with        electrophilic reagents; and    -   (ii) blending said combination to obtain a homogeneous wettable        powder (WP) formulation.

According to a fifth aspect of the present invention, there is provideda method of making an agrochemical formulation comprising the steps of:

-   -   (i) combining at least one insoluble material suitable for        agricultural use with at least one dispersant comprising a        copolymer wherein said copolymer comprises a residue of a first        comonomer and a residue of a second comonomer, wherein said        first comonomer is an α,β-unsaturated oxyacid or anhydride and        said second comonomer is an olefin having at least one        polymerizable double bond and wherein at least one of said first        comonomer and said second comonomer is substituted, wherein the        substituents for said first comonomer are selected from the        group consisting of esters, amides, thioesters and other        functional groups derived from reaction with nucleophilic        reagents and wherein the substituents for the second comonomer        are selected from the group consisting of epoxides; sulfonates;        esters; amides; and optionally substituted pendent aromatic and        heteroaromatic groups wherein said optional substituents are        selected from the group consisting of sulfonates, nitrates,        phosphates and other substituents derived from reaction with        electrophilic reagents;    -   (ii) agglomerating said combination to form discrete granular        materials; and    -   (iii) drying said granular materials to obtain a water        dispersible granule WG formulation.

According to a sixth aspect of the present invention, there is provideda formulation produced by the process of the second, third, fourth andfifth aspects.

According to a seventh aspect of the present invention, there isprovided an agricultural formulation comprising at least one insolublematerial and at least one dispersant comprising a copolymer wherein saidcopolymer comprises a residue of a first comonomer and a residue of asecond comonomer, wherein said first comonomer is an α,β-unsaturatedoxyacid or anhydride and said second comonomer is an olefin having atleast one polymerizable double bond and wherein at least one of saidfirst comonomer and said second comonomer is substituted, wherein thesubstituents for said first comonomer are selected from the groupconsisting of esters, amides, thioesters and other functional groupsderived from reaction with nucleophilic reagents and wherein thesubstituents for the second comonomer are selected from the groupconsisting of epoxides; sulfonates; esters; amides; and optionallysubstituted pendent aromatic and heteroaromatic groups wherein saidoptional substituents are selected from the group consisting ofsulfonates, nitrates, phosphates and other substituents derived fromreaction with electrophilic reagents.

According to an eighth aspect of the present invention, there isprovided a method of treatment of a substrate with an insoluble materialcomprising the following steps:

-   -   (i) preparing a formulation comprising at least one insoluble        material and at least one dispersant comprising a copolymer        wherein said copolymer comprises a residue of a first comonomer        and a residue of a second comonomer, wherein said first        comonomer is an α,β-unsaturated oxyacid or anhydride and said        second comonomer is an olefin having at least one polymerizable        double bond and wherein at least one of said first comonomer and        said second comonomer is substituted, wherein the substituents        for said first comonomer are selected from the group consisting        of esters, amides, thioesters and other functional groups        derived from reaction with nucleophilic reagents and wherein the        substituents for the second comonomer are selected from the        group consisting of epoxides; sulfonates; esters; amides; and        optionally substituted pendent aromatic and heteroaromatic        groups wherein said optional substituents are selected from the        group consisting of sulfonates, nitrates, phosphates and other        substituents derived from reaction with electrophilic reagents;    -   (ii) dispersing said formulation in an aqueous medium; and    -   (iii) applying the dispersed formulation to the substrate.

The derivatisation of the copolymer is of central importance to theinvention herein described. While not wishing to be bound by theory, itappears that in addition to the enhanced solubility in water, it mayconfer additional polarity or charge density to the dispersant such asto enhance its performance. Further it may lead to better conformationalalignment of the copolymer and therefore the copolymer is more readilysoluble and may more readily align itself with surfaces. We have foundthat a non alternating polymer which is unsuitable for use as adispersant when used as an alkali metal or quaternary ammonium saltderivative is significantly improved in dispersant performance whenderivatised according to the present invention.

The first comonomer for use in the present invention may be anycomonomer polymerizable with the second comonomer. Examples of suitablepreferred first comonomers of the present invention include fumaricacid, maleic acid and anhydrides, and the esters, amides and imidesderived from them, itaconic acid and anhydride and the correspondingesters amides and imides derived from them, acrylic and methacrylicacids and the corresponding esters and amides derived from them,vinylphosphonic acid and the corresponding esters and amides derivedfrom it and ethylene sulphonic acid and the esters and amides derivedfrom it.

The second comonomer for use in the present invention is an olefinhaving at least one polymerizable double bond which may be substitutedas defined herein.

The second comonomer for use in the second embodiment of the presentinvention may be an alicyclic monomer having a polymerizable exo-cyclicdouble bond. It will be understood that by alicyclic monomer is meant analiphatic cyclic monomer containing moieties such as a cyclic alkyl,cyclic alkenyl or heterocyclic groups and which may comprise one or morecarbocyclic or heterocyclic rings. It will be understood that byexo-cyclic is meant an alkylidene substituted cyclic structure.Alicyclic monomers having a polymerizable exo-cyclic double bond mayoptionally be substituted. Alicyclic monomers having a polymerizableexo-cyclic double bond of the present invention may include, forexample, β-pinene, 5-ethylidene-2-norbornene, methylene cyclohexane andmethylene cyclopentane. The most preferred alicyclic monomer having apolymerizable exo-cyclic double bond.

The second comonomer for use in the second embodiment of the presentinvention may be an alicyclic monomer having a polymerizable endo-cyclicdouble bond. The term alicyclic monomer is as hereinabove defined. Itwill be understood that by endo-cyclic is meant the polymerizable doublebond has both ends (or termini) forming part of the cyclic structure ofthe alicyclic monomer. Alicyclic monomers having a polymerizableendo-cyclic double bond may optionally be substituted. Alicyclicmonomers having a polymerizable endocyclic double bond may includesubstituted and unsubstituted norbornene, cyclopentadiene andsubstituted cyclopentadienes, substituted and unsubstituteddicyclopentadienes, cyclohexenes, furans and indenes. Most preferred ofthe above monomers containing an endo-cyclic double bond aredicyclopentadiene and dimethyldicyclopentadiene.

The second comonomer for use in the second embodiment of the presentinvention may be an α-olefin having at least one cyclic substituent. Itwill be understood that by α-olefin is meant an olefinic compound havinga terminal double bond. Suitable cyclic substituents include benzene andsubstituted benzene, cyclopentane, cyclohexane, and othercycloaliphatics, heterocyclics, heteroaromatics, aromatics andpolyaromatics. Examples of suitable α-olefinic cyclic compounds includelimonene and similar terpenes, vinyl cyclohexanes, vinyl cyclohexenes,vinyl pyridines, vinyl thiophenes, vinyl naphthalenes, vinyl furans,vinyl pyrans and, vinyl pyrrolidones. Most preferred α-olefin cyclicmonomers include limonene, vinyl naphthalene, vinyl pyrrolidone, allylglycidyl ether and vinyl cyclohexene.

The second comonomer of the second embodiment of the present inventionmay be an α-olefin having an alkyl group such as diisobutylene,isobutylene, n-octene, n-decene, allyglycidylether orvinylisobutylether. The second comonomer may also be an internal olefin.

Preferred examples of the first comonomer may be described as havingstructure I:

wherein R₁ is a metal, quaternary ammonium, phosphonium or sulphoniumresidue, R₂ is hydrogen, C₁ to C₄ alkyl, or CH₂CO₂H, Y is a carbon atom,the group O═S, or the group POR where R is a hydrogen atom or alkylradical having from 1 to 10 carbon atoms (or carboxylated such radical),R₃ is hydrogen, and R₄ is hydrogen, an alkyl radical or a carboxylicacid derivative of form II:

wherein R₅ is OR₆, NR₆R₇ or SR₆, wherein R₆ and R₇ are hydrogen, alkyl,O-alkyl, or alkyl groups with a hetero atom substituent. The secondcomonomer may be alternatively described as a residue having formulaIII:

wherein R₈ represents hydrogen, a straight or branched chain alkyl offrom 1-4 carbon atoms, R₉ represents hydrogen, a branched chain alkylradical of from 1-12 carbon atoms, or a cycloalkyl radical, and/or avinyl compound of formula IV:

wherein R₁₀ is a straight or branched chain alkyl radical of from 1-4carbons and R₁₁ is given by formula V, VI or VII:

wherein R₁₂ represents one or more alkyl radicals or one or more of H,Cl, OR, SO₃R₁, NO₂ and PO₃R₁, and X is a hetero atom other than carbon;and/or an olefin shown by formula VIII:

wherein R₁₃ is Cl, SO₃R₁, alkyl, O-alkyl or O-aryl, R₁₄ represents from4-20 carbon atoms such as to make a cyclic or polycyclic alkane orpolyalkenyl compound, and R₁₅ is an epoxide or SO₃R₁ reacted with anunsaturated portion of the ring comprising R₁₄; and/or an exocyclicolefin shown by formula IX:

and/or an internal olefin shown by formula X:

where R₉ is the same or different and as hereinabove defined.

The dispersant copolymers of the present invention may also includecopolymers being the water soluble derivatives of a combination of anunsaturated α,β-unsaturated oxyacid or anhydride and another olefinicmonomer, not limited to being of an alternating structure, that may havebeen derivatised post copolymerisation such as to provide the necessarysubstituents which may enhance water solubility and regularity of chargeor polarity on the polymer. Such derivatisation includes that obtainedfrom reaction of groups pendant to the copolymer such as acids and acidderivatives with nucleophilic reagents such as alcohols, amines andthiols to give esters, amides and thioesters respectively.

In a further form of derivatisation copolymers with residual reactiveunsaturation may be reacted with electrophilic or radical reagents suchas peroxides or sulphite to give epoxides and sulphonates respectively.

In a special case of the above, copolymers with pendant aryl orheteroaryl groups can be made to undergo electrophilic aromaticsubstitution with sulphonating, nitrating and phosphating reagents.

While not wishing to be bound by theory, copolymers with hydroxyl groupscan be esterified with acids including carboxylic, sulphuric andphosphoric acids. The alternating, or repeating, units are preferablymonomers but may also be dimers, trimers or small oligomers.

While not wishing to be bound by theory, it is believed that thestiffness of the polymer molecule is relates to its performance as adispersant. It is believed that improved dispersant performance isrelated to the degree of steric hindrance and the resistance ofcopolymer to free rotation.

The copolymer may contain additional comonomer residues. For example,the addition of a small amount, say less than 10%, of methylmethacrylate will not substantially change the character of thederivatised copolymer. The copolymer may contain residues of additionalad olefin comonomers whether derivatised or not. Suitable copolymers foruse in the present invention also include copolymers of three or morecomonomers. Additional comonomers may also be incorporated into thederivatised copolymer without changing the character of the polymer.

While not wishing to be bound by theory it appears that where aconsistent hydrophobic polymer backbone is provided in the presence ofregularly spaced anionic charge or steric barrier along the polymer, theimproved dispersant performance is preserved.

The preferred molecular weights of the copolymers of the presentinvention are in the range of from 1000 to 90000 daltons. We have foundthat certain higher molecular weight copolymers show a certain degree ofintractability in solution and our more preferred range is from1000-30000 daltons, even more preferred is 1000-10000 daltons.

We have found that agriculturally acceptable salts of copolymers asdescribed herein for use as dispersants in agricultural compositionsprovide improved and consistent dispersant performance when compared toconventionally used dispersants such as sulfonated alkylnaphthaleneformaldehyde condensate salts.

It is surprising that copolymers as described herein give enhancedperformance when compared to previously described dispersants structuresin the prior art such as for example diisobutylene, isobutylene andstyrene copolymers with maleic anhydride while still other derivativesdescribed in those same publications, cannot be reasonably used asdispersants in agricultural applications at all. For example we havefound that styrene-maleic anhydride copolymer derivatives resulted in aless stable and sometimes unstable dispersion. Further, copolymers ofmethylvinylether and maleic anhydride also afford an unstabledispersion. Similarly some linear α-olefin maleic anhydride derivativessuch as those derived from n-octene and n-decene also yielded unstabledispersions affording poor suspensibility. It was found that thesubstituted or derivatised copolymers of the above copolymers accordingto the present invention showed improved performance not limited bypossible effects of molecular weight and/or molecular conformation whichappear to limit the performance of the parent copolymer.

The performance of the copolymers described herein has been observed atdifferent dispersant concentrations in WP and WG formulations to exhibitimproved storage stability. Also we have found that in many cases it ispossible to lower the dispersant concentration from normally acceptedlevels and retain an acceptable suspensibility result, thereby achievingmore efficient the surface coverage of the dispersant. In practicalterms this means the dispersant will be more cost effective to the enduser. When the use rate of copolymers is compared to that of adiisobutylene maleic anhydride sodium salt of similar molecular weighttypically we have found that the copolymers of this invention may giveacceptable stability at a concentration lower than the correspondingdiisobutylene derivative. In addition the formulations typically showimproved dispersibility. When compared to sulfonated alkyl naphthaleneformaldehyde condensates, suspensibility is significantly improved, evenat lower concentrations.

Methods for making such copolymers of the second embodiment of thepresent invention from first and second comonomers will be well known tothose skilled in the art of polymer synthesis. The comonomers of thepresent invention may be substituted prior to or post polymerizationwith methods which will be appreciated by those skilled in the art.

The dispersant system used in embodiments of the present invention maybe a mixture of the copolymer as herein described with other dispersantsknown to those skilled in the art, including alkyl substituted andunsubstituted sulfonated naphthalene formaldehyde condensate salts,alkyl substituted and unsubstituted phenol formaldehyde condensatesalts, lignosulphonate salts, polyacrylate salts, and previouslydescribed α-olefinic unsaturated dicarboxylic acid copolymerderivatives.

In agrochemical applications, a wide variety of insoluble materials suchas active principals are delivered in aqueous suspension. Activeprincipals such as those used in WP, WG and SC formulations aregenerally insoluble at ambient temperatures. Water insoluble materialswhich may advantageously be used in WP, WG and SC formulations includeherbicides, insecticides, fungicides, biocides, molluscicides,algaicides, plant growth regulators, anthelmintics, rodenticides,nematocides, acaricides, amoebicides, protozoacides, crop safeners andadjuvants. Examples of such actives commonly granulated or made aspowders in agriculture include: triazine herbicides such as simazine,atrazine, terbuthylazine, terbutryn, prometryn and ametryn, ureaherbicides such as diuron and fluometron, sulphonyl urea herbicides suchas chlorsulfuron, metsulfuron methyl, nicosulfuron and triasulfuron,sulphonanilide herbicides such as flumetsulam, organophosphateinsecticides such as azinphos methyl, chlorpyrifos, sulprofos andazamethiphos, carbamate insecticides such as aldicarb, bendiocarb,carbaryl and BPMC, synthetic pyrethroids such as bifenthrin, as well asvarious types of fungicides including dimethomorph, benomyl,carbendazim, mancozeb, triazoles such as hexaconazole and diniconazole,acaricides such as propargite. A list of such products can be drawn fromthe Pesticide Dictionary (contained in the Farm Chemicals Handbook) orthe British Crop Protection Society: Pesticides Manual.

In addition, some fertilizers and also water soluble active principlesmay use water dispersible formulations either by addition of inertcarriers for convenience in handling or to aid in a controlled releaseformulation.

A wide variety of other insoluble materials are used in agriculturalapplications including fillers and carriers, for example but not limitedto, natural and synthetic silicates and silicate minerals, mineraloxides and hydroxides and also natural and synthetically derived organicmaterials. Such materials may be added as porous carriers, as moistureinhibition agents, to aid binding or agglomeration properties of aformulation or simply to fill a formulation to a convenient weight.Examples of such fillers may include natural silicates such asdiatomacious earth, synthetic precipitated silicas, clays such askaolin, attapulgites and bentonites, zeolites, titanium dioxide, ironoxides and hydroxides, aluminium oxides and hydroxides, or organicmaterials such as bagasse, charcoal, or synthetic organic polymers.These other insoluble materials may be readily dispersed in accordancewith the present invention.

An additional agent conventionally used in combination with dispersantsused in the above formulations is a surfactant wetting agent. The roleof the wetting agent in the case of SC formulations is to aid removal ofair from particle surfaces during manufacture and to aid dilution inwater. In the case of WP formulations the role of the wetter may be toaid penetration of the solids into water, while in the case of WGformulations it may aid penetration of the granules into water and aiddisintegration of granules back to primary particle size. In some casesthe dispersant may itself function as a suitable wetting agent while inothers the dispersant may show an antagonistic effect on the wetter. Asa further embodiment of the present invention at least one surfactantwetting agent may be selected from the group consisting of analkylpolysaccharide; di or mono alkyl sulphosuccinate derivative; anonionic surfactant loaded onto an inert silicate carrier; and anon-ionic surfactant delivered in the form of a urea surfactant complex.

The step of dispersing the formulation in an aqueous medium may beachieved by any convenient means dependent on the nature of theformulation. It is desirable that the dispersion of the formulation inan aqueous solution may be conducted either by hand or with a minimum ofmechanical agitation. Mechanical agitation may include stirring, mixing,blending and other similar processes.

The suspension of insoluble material in aqueous medium will be typicallyused for the treatment of a substrate such as plant or otheragricultural medium. The application of the suspension onto thesubstrate may be achieved by any convenient means, including spraying,and the like. Granules are generally dispersed in water prior to beingsprayed by the farmer. Farm sprays may be as a small back-pack handsprayor a large boom spray or other convenient means. Aerial spraying is alsosometimes used.

Formulations of the present invention may also be applied to thesubstrate directly, prior to dispersion. The subsequent application ofrain or other aqueous media is sufficient for the formulation of thesuspension of particulate material.

The present invention is described with reference to WP, WG and SCformulations. In each case, formulations provide a stable aqueousdispersion of finely milled insoluble hydrophobic particles. Thestability properties of the dispersion and hence the effectiveness ofthe dispersion can be measured by means of a suspensibility test asdescribed by the CIPAC test MT 15.1. In this test the volume fraction ofsuspended material is compared to that which has settled out due togravity after 30 minutes. Typically a reported percentage suspersiblityabout 80% would be considered as, an effective dispersant for WG and WPformulations, while in excess of 90% would be expected for an SCformulation. Another measure of the stability of the dispersion is thedegree to which particles remain non aggregated. This may also be aproperty of the even distribution of the dispersant in the formulation.The degree to which particles may be aggregated is often measured by awet sieve retention test as described in CIPAC test MT 59.3. In thistest the dispersed solid is poured through a series of fine sieves andretained material is measured as a fraction of the total amount ofdispersed material. Formation of such aggregates is a major problemobserved in WG formulations and to a lesser extent in WP formulations.

Generally WP formulations are produced by milling the active principleeither alone or in combination with fillers, dispersants and/orsurfactant wetters to a suitable particle size, typically in the 5-15 μmrange. The milled material is then dry blended with a surfactant wetter,and/or dispersant if not already present or with additional dispersantsand/or surfactant wetters to give a homogeneous composition. The powderformulation is assessed for wettability according to a method such asCIPAC MT 53.5.1 and suspensibility as per CIPAC MT 15.1. A formulationwill desirably have a wettability of less than 1 minute and asuspensibility above 80%. Below 60% would generally be consideredunacceptable. Results which might be commercially acceptable are eitherdetermined by the local registration authority or by the standards setby the formulators themselves.

In the case of WG formulations a suitably milled active ingredient withor without other fillers, typically of particle size 5 to 15 μm, may bemixed with one or more surfactant wetters and one or more dispersants.Typically an excess of water is added to bind the particles togetherinto agglomerates. The excess water is later reduced by suitable airdrying techniques to an optimal level.

The agglomerates are typically granulated using one of many techniquesincluding pan granulation, drum granulation, fluid bed granulation,spray drying, tableting or extrusion techniques which are well known tothose skilled in the art.

The wetter and dispersant may either be powder blended with the activeingredient or alternatively blended as an aqueous solution in the waterused to aid agglomeration. The active ingredient, fillers, wetter anddispersant may also be milled together in one operation prior toaddition of water.

For a WG formulation to be acceptable an additional requirement is thatthe said granules should readily disperse in water back to the primarydispersed particle size within a short period. This property is known asdispersibility and in describing the current invention it is measured asthe time taken for granules to disperse back to primary particle size inwater under a standard degree of agitation. A dispersion time of lessthan one minute is desirable, 20 seconds is excellent and 2 minutes ispoor. Desirably the granules should also have good suspensibility.Suspensibility is typically tested using CIPAC MT 15.1. Above 80% is adesirable result, less than 60% is generally regarded as undesirable. Inmany cases when testing granules a so-called maximum surface coverageresult is often obtained. This is where the suspensibility results reacha maximum level then plateau. Adding more dispersant will not generallyimprove the result. This phenomenon is thought to be due to the particlesize distribution of the material. Usually there is a given number ofparticles which are of such a size that they will settle regardless oftype and concentration of dispersant.

Desirably the granules should have low wet sieve retention. Wet sieveretention is typically tested using CIPAC MT 59.3. For the 150 μm sieveless than 0.1% retained material is desirable. Less than 0.02% is moredesirable. Likewise for the 53 μm sieve less than 0.6% is desirable,anything less than this is more desirable.

A further desirable property of a WG formulation is that the granulesshould be non-dusty and resistant to attrition. This is often a propertyof the method of granulation used and the level of compaction thereobtained. Often there is an observed tradeoff between the dispersibilityproperties of a WG formulation and the level of compaction and attritionresistance. Attrition resistance may be measured by subjecting granulesto a set degree of agitation and measuring the level of smallerparticles generated by means of passing through sieves of various sizes.

Storage stability may be tested by storage at 50 degrees celsius andtested as above at 1 month and 3 month intervals to determine if anyproperties have changed significantly.

Preferably, the granules should maintain these properties on storage.Surprisingly, it has been observed that, upon prolonged storage, solidformulations such as WP and WG formulations containing dispersants suchas those described herein are not as susceptible to deterioration indispersability and suspensibility as formulations of the prior art.

We have also found that WP and WG formulations which incorporate thedispersants described herein require typically less dispersant, than forpresently known WP and WG formulations.

As a further embodiment of the present invention in the case of WP andWG formulations the dispersants herein described may be combined withsurfactant wetting agents selected from the classes comprisingalkylpolysaccharides, dialkyl and monoalkylsulphosuccinate salts,nonionic surfactants loaded onto porous silicate carriers and ureasurfactant complexes of non-ionic surfactants. The wetting agent may becombined in such formulations at a rate in excess of 1% w/w andpreferably less than 3% w/w. Most preferred from the alkylpolysaccharideclass of wetting agents are alkylpolyglucosides derived from reactionwith glucose and a primary hydrocarbon alcohol. Even more preferred arethe highly crystalline derivatives such as obtained from ECOTERIC AS 20and ECOTERIC AS10 (Huntsman Corporation Australia Pty Ltd). Mostpreferred from the monoalkylsulphosuccinate class are sodium orpotassium salts of cyclohexyl, iso-otyl and n-octyl sulphosuccinate.Most preferred from the dialkylsulphosuccinate class are sodium orpotassium salts of dicyclohexyl, diisooctyl and di-n-octylsulphosuccinates. Most preferred from the class of nonionic surfactantsloaded onto insoluble porous silicate carriers are ethoxylatedsurfactants loaded onto carriers such as TERIC 157 (Huntsman CorporationAustralia Pty Ltd). Most preferred wetting agents from the ureasurfactant complexes are urea adducts of alcohol ethoxylate surfactantssuch as TERWET 7050 (Huntsman Corporation Australia Pty Ltd). Thewetters herein described show good wettability and dispersibility forthe formulations and have the additional advantage of showing storagestability in combination with the copolymer dispersants described.Whereas by comparison some commonly used WG and WP wetters such asalkylnaphthalene sulphonate salts and lignosulphonate salts have beenfound to show poor storage stability.

In the case of SC formulations in the present invention an activeingredient is typically added to water containing a dispersant,preferably with a surfactant wetting agent together with a conventionalnon-ionic dispersant. A humectant may also be included. A dispersion isformed using high shear mixing. The dispersion is then milled by any oneof several means of wet milling so that the mean particle size of thedispersed solid is below 5 μm more typically in the range of from 1 to 3μm. The resulting product is known as a millbase and may be modifiedwith additives such as antifreeze, thickeners and antisettling agents,biocides and colouring agents may be added. For an SC formulation to beacceptable it should not show a high degree of thickening, settling orgrowth of aggregates over time. These physical properties can beassessed by visual observation.

SC's generally require good viscosity and storage stability. Storagestability is usually assessed as degree of top settling or syneresis,sedimenting or “claying” which is the tendency to form a sticky layer onthe bottom and “bleeding” which is the tendency of the dispersion toseparate without necessarily displaying even settling. Redispersibilityis also important. These may also be assessed visually.

For SC formulations in the case of dispersants described herein onlycertain dispersant copolymers are suitable. When used alone, somedispersant copolymer derivatives give a viscosity of slurry premixunsuitable for milling so it is preferable to combine the dispersantwith another fast acting well known dispersant such as an EO/PO blockco-polymer type dispersant. While not wishing to be bound by theory itappears that the dispersant needs time to migrate to the surface of thedispersed particles. The dispersant copolymers are used synergisticallywith other known dispersants in some cases.

While the present invention has been described with reference toagrochemical formulations, it will be apparent that the improvements indispersibility and suspensibility will render the present inventionuseful in other applications. The present invention will now be furtherdescribed with reference to the following non-limiting examples andfigures. All percentages recited herein are by weight of the totalcomposition unless otherwise specified.

EXAMPLE 1

A Simazine 900 g/kg WG formulation of the following composition wasprepared.

Simazine tech. (98% w/w) 91.8% w/w MORWET EFW 1.5 (Witco Corp.)DISPERSANT 6.2 Water 0.5%

The dispersant used was an alkylhaphthalene formaldehyde condensatesalt, SCS 2258 (ICI Surfactants). The granules were prepared by blendingthe solids with approximately 15% by weight of water such as to give aplastic premix which was then extruded using a Fuji-Paudal laboratoryscale extrusion granulator. The resulting granules were then dried bymeans of a fluid bed drier back to a water content of approximately 0.5%w/w.

The resulting WG was tested for dispersibility by recording the time inseconds required for total disintegration under uniform agitation. Thesuspensibility was tested according to CIPAC MT 15.1 and the wet sieveretention was tested using 150 micron and 53 micron sieves according toCIPAC MT 59.3. Results are recorded in TABLE 1.

EXAMPLE 2

A simazine 900 g/Kg WG was prepared and tested as described in example 1where the dispersant used POLYFON H (Westvaco Corp), a lignosulphonatesalt. The results are described in TABLE 1.

EXAMPLE 3

A Simazine 900 g/kg WG formulation of the following composition wasprepared:

Simazine tech. (98% w/w) 91.8% w/w ATPLUS G73050 1.5 (now sold under thetrademark TERWET 7050, Huntsman Corporation Australia Pty Ltd)DISPERSANT 3.1 Kaolin 3.1 Water 0.5%

The dispersant used was the sodium salt of an alternating copolymer ofn-octene and maleic anhydride of approximate molecular weight 20,000 to30,000. The granules were prepared and tested in the manner described inExample 1. The results are shown in TABLE 1.

EXAMPLE 4

A Simazine 900 g/kg WG formulation was prepared and tested in the mannerdescribed in Example 3 with the dispersant being the sodium salt of acopolymer of n-decene and maleic anhydride. Results are shown in TABLE1.

EXAMPLE 5

A Simazine 900 g/kg WG formulation was prepared and tested in the mannerdescribed in Example 3 with the dispersant being the sodium salt of acopolymer of diisobutylene and maleic anhydride of approximate molecularweight 20,000 to 30,000. Results are shown in TABLE 1.

EXAMPLE 6

A WG formulation was prepared and tested as described in Example 3 withthe dispersant being the sodium salt of SMA 1000 (Atochem Inc) which isa 1:1 molar ratio copolymer of styrene and maleic anhydride. Results areshown in TABLE 1.

EXAMPLE 7

A WG formulation was prepared and tested as described in Example 3 withthe dispersant being the sodium salt of SMA 3000 (Atochem Inc) which isa 3:1 molar ratio copolymer of styrene and maleic anhydride. Results areshown in TABLE 1.

EXAMPLE 8

A WG formulation was prepared and tested as described in Example 3 withthe dispersant being the sodium salt of GANTREZ AN 119 resin (RhodiaInc) which is a copolymer of methylvinyl ether and maleic anhydride.Results are shown in TABLE 1.

EXAMPLE 9

A Simazine 900 g/kg WG formulation of the following composition wasprepared:

Simazine tech. (98% w/w) 91.8% w/w ATPLUS G73050 1.5 (now sold under thetrademark TERWET 7050, Huntsman Corporation Australia Pty Ltd)DISPERSANT 3.1 Kaolin 3.1 Water 0.5%

The dispersant used was the sodium salt of a copolymer of n-octene andmaleic anhydride derivatised by reaction with morpholine to give amorpholine amide derivative. The granules were prepared and tested inthe manner described in Example 1. Results are shown in TABLE 2.

EXAMPLE 10

A Simazine 900 g/kg WG formulation was prepared and tested in the mannerdescribed in Example 9 with the dispersant being the sodium salt of themorpholine amide derivative of a co-polymer of n-decene and maleicanhydride. Results are shown in TABLE 2.

EXAMPLE 11

A Simazine 900 g/kg WG formulation was prepared and tested in the mannerdescribed in Example 9 with the dispersant being the sodium salt of themorpholine amide derivative of SMA 1000 (Atochem Inc), a 1:1 molar ratiocopolymer of styrene and maleic anhydride. Results are shown in TABLE 2.

EXAMPLE 12

A Simazine 900 g/kg WG formulation was prepared and tested in the mannerdescribed in Example 9 with the dispersant being the sodium salt of themorpholine amide derivative of SMA 3000 (Atochem Inc), a 3:1 molar ratiocopolymer of styrene and maleic anhydride. Results are shown in TABLE 2.

EXAMPLE 13

A Simazine 900 g/kg WG formulation was prepared and tested in the mannerdescribed in Example 9 with the dispersant being the sodium salt of thearomatic sulphonated derivative of SMA 1000 (Atochem Inc), a 1:1 molarratio copolymer of styrene and maleic anhydride. Results are shown inTABLE 2.

EXAMPLE 14

A Simazine 900 g/kg WG formulation was prepared and tested in the mannerdescribed in Example 9 with the dispersant being the sodium salt of theco-polymer of alphamethylstyrene and maleic anhydride derivatised withammonia to give the corresponding monoamide. Results are shown in TABLE2.

EXAMPLE 15

A Sinazine 900 g/kg WG formulation was prepared and tested in the mannerdescribed in Example 9 with the disperant being the sodium salt of thecopolymer of alpharnethylstyrene and maleic anhydride derivatised withethanolamine to give the corresponding ethanolamide. Results are shownin TABLE 2.

EXAMPLE 16

A Simazine 900 g/kg WG formulation was prepared and tested in the mannerdescribed in Example 9 with the dispersant being the sodium salt of thecopolymer of alphamethylstyrene and maleic anhydride derivatised withn-butylamine to give the corresponding n-butylamide. Results are shownin TABLE 2.

EXAMPLE 17

A Simazine 900 g/kg WG formulation was prepared and tested in the mannerdescribed in Example 9 with the dispersant being the sodium salt of thecopolymer of alphamethylstyrene and maleic anhydride derivatised withmorpholine to give the corresponding morpholine amide. Results are shownin Table 2.

EXAMPLE 18

A Simazine 900 g/kg WG formulation was prepared and tested in the mannerdescribed in Example 9 with the dispersant being the sodium salt of thecopolymer of dicyclopentadiene and maleic anhydride derivatisedmorpholine to give the corresponding amide. Results are shown in TABLE2.

EXAMPLE 19

A Simazine 900 g/kg WG formulation was prepared and tested in the mannerdescribed in Example 9 with the dispersant being a sulphonatedderivative of the sodium salt of the copolymer of dicyclopentadiene andmaleic anhydride. Results are shown in TABLE 2.

EXAMPLE 20

A Simazine 900 g/kg WG formulation was prepared and tested the mannerdescribed in Example 9 with the dispersant being a sulphonatedderivative of the sodium salt of the copolymer ofdimetyldicyclopentadiene and maleic anhydride. Results are shown inTABLE 2.

EXAMPLE 21

A Simazine 900 g/kg WG formulation was prepared and tested in the mannerdescribed in Example 9 with the dispersant being the sodium salt of thecopolymer of dimethyldicyclopentadiene and maleic anhydride derivatisedwith morpholine to give the corresponding morpholine amide. Results areshown in TABLE 2.

EXAMPLE 22

A Simazine 900 g/kg WG formulation was prepared and tested in the mannerdescribed in Example 9 with the dispersant being the sodium salt of themorpholine amide derivative of Gantrez AN119(Rhodia Corp.), a copolymerof methylvinyl ether and maleic anhydride Results are shown in TABLE 2.

EXAMPLE 23

A Simazine 900 g/kg WG formulation was prepared and tested in the mannerdescribed in Example 9 with the dispersant being the sodium salt of thecyclohexyl amide derivative of Gantrez AN119(Rhodia Corp), a copolymerof methylvinyl ether and maleic anhydride Results are shown in TABLE 2.

EXAMPLE 24

An Atrazine 900 g/Kg SC formulation of the following composition wasprepared.

Atrazine tech. 97% w/w 51.5% w/v Monoethylene glycol 4.0 DISPERSANT 4Silicone antifoam 0.2 Rhodopol 23 0.2 (Rhodia Inc.) Proxel GXL 20 0.1(Zeneca plc) Water. 55.0

The dispersant used was the sodium salt of a sulphonated copolymer ofdicyclopentadiene and maleic anhydride. The SC was prepared bydissolving the monoethylene glycol, ATLOX 4896A and DISPERSANT in 85% ofthe water and adding the Atrazine tech. and antifoam with vigorousmixing to form a slurry or millbase premix. The premix is then milledusing a Dynomill laboratory scale bead mill to give a suitable particlesize distribution of >98% of particles below 5 microns. The millbasethus obtained was then blended with Proxel GXL 20(Zeneca plc) andRodopol 23(Rhodia Inc.) in a premix and then made up to the desiredvolume with the remaining water and mixed to a homogeneous mixture. TheSC thus obtained was of usable viscosity and was found to be storagestable after storage at 2 degrees C. and 50 degrees C. for one month,with minimal syneresis and thickening and no claying, sedimentation oraggregates being observed.

TABLE 1 WDG Results from Prior Art Dispersibility Suspensibility WetSieve Retention (%) Example (Seconds) (%) 150 μm 50 μm No. T₀ T₁ T₃ T₀T₁ T₃ T₀ T₁ T₃ T₀ T₁ T₃ 1 52 46 44 82 63 69 0.087 0.41 2.2  0.033 1.531.70 2 58 45 46 80 68 70 0.029 1.09 0.92 0.486 4.10 4.70 3 36 — — 39 — —— — — — — — 4 33 — — 59 — — 0.002 — — 0.042 — — 5 60 54 50 72 78 710.02  0.02  0.016 0.15  0.21 0.28 6 55 — — 31 — — 0.027 — — 0.0957 >280  — — <10  — — — — — — — — 8 53 — — 48 — — 0.002 — — 0.085 — — T₀initial results T₁ after 1 month storage at 50° C. T₃ after 3 monthsstorage at 50° C.

TABLE 2 WG Formulations using Dispersants of Second Embodiment Dispers-Suspens- Example ibility ibility Wet Sieve Retention (%) No. T₀ T₁ T₀ T₁T₀ T₁ T₀ T₁  9 71 45 87 82 0.10  0.10  0.068 0.21  10 95 85 75 68 0.0050.001 0.042 0.051 11 67 62 85 83 0.005 0.002 0.060 0.118 12 28 26 84 880.001 0.005 0.039 0.052 13 58 56 85 83 0.038 0.068 0.195 0.140 14 68 6883 83 0.001 0.004 0.051 0.054 15 10 — 70 — 0.05  — 2.79  — 16 68 40 8177 0.005 0.012 0.044 0.092 17 53 120  86 81 0.005 0.21  0.065 0.13  1840 32 87 85 0.004 0.007 0.051 0.313 19 26 33 86 86 0.001 0.001 0.0450.053 20 57 44 85 86 0.002 0.008 0.064 0.199 22 57 36 87 72 0.02  0.55 0.06  5.64  23 69 95 86 83 0.033 0.033 0.144 0.88  21 32 30 87 87 0.0010.005 0.054 0.048 T₀ initial results T₁ after 1 month storage at 50° C.*Data not yet available —Testing discontinued

Those skilled in the art will appreciate that the invention describedherein is susceptible to variations and modifications other than thosespecifically described. It is to be understood that the inventionincludes all such variations and modifications which fall within itsspirit and scope. The invention also includes all of the steps,features, compositions and compounds referred to or indicated in thisspecification, individually or collectively, and any and allcombinations of any two or more of said steps or features.

1. A method of dispersing a solid insoluble material in an aqueoussolution comprising the following steps: (i) providing a formulationcomprising at least one finely divided solid insoluble material and atleast one dispersant comprising a water soluble copolymer wherein saidcopolymer comprises a residue of a first comonomer and a residue of asecond comonomer, wherein said first comonomer is an α,β-unsaturatedoxyacid or anhydride and said second comonomer is an olefin having atleast one polymerizable double bond and wherein the second comonomer isselected from the group consisting of β-pinene,5-ethylidene-2-norbornene, methylene cyclohexane and methylenecyclopentane; (ii) dispersing said formulation in an aqueous medium. 2.A method according to claim 1 wherein the copolymer contains additionalcomonomer residues which will not substantially change the character ofthe copolymer.
 3. A method of dispersing a solid active water-insolubleagrochemical principal in an aqueous solution comprising the followingsteps: (i) providing a formulation comprising at least one finelydivided solid active water-insoluble agrochemical principal and at leastone dispersant comprising a water soluble copolymer wherein saidcopolymer comprises a residue of a first comonomer and a residue of asecond comonomer, wherein said first comonomer is an α,β-unsaturatedoxyacid or anhydride and said second comonomer is an olefin having atleast one polymerizable double bond and wherein at least one of saidfirst comonomer and said second comonomer is substituted, wherein thesubstituents for said first comonomer are selected from the groupconsisting of esters, amides, thioesters and other functional groupsderived from reaction with nucleophilic reagents and wherein thesubstituents for the second comonomer are selected from the groupconsisting of epoxides; sulfonates; esters; amides; and optionallysubstituted pendent aromatic and heteroaromatic groups wherein saidoptional substituents are selected from the group consisting ofsulfonates, nitrates, phosphates and other substituents derived fromreaction with electrophilic reagents; with the provisos that (a) whenthe second comonomer is sulphonated styrene or sulphonated isobutylene,the first comonomer is substituted, (b) when the second comonomer issulphonated styrene, the first comonomer is not alkyl acrylate or alkylmethacrylate, and (c) when the first comonomer is maleic anhydride, thesecond comonomer is not styrene; (ii) dispersing said formulation in anaqueous medium.
 4. A method according to claim 3 wherein the firstcomonomers are selected from the group consisting of fumaric acid,maleic acid and anhydrides, and the esters, amides and imides derivedfrom them, itaconic acid and anhydride and the corresponding estersamides and imides derived from them, acrylic and methacrylic acids andthe corresponding esters and amides derived from them, vinylphosphonicacid and the corresponding esters and amides derived from it andethylene sulphonic acid and the esters and amides derived from it.
 5. Amethod according to claim 3 wherein the second comonomer is selectedfrom the group consisting of β-pinene, 5-ethylidene-2-norbornene,methylene cyclohexane and methylene cyclopentane.
 6. A method accordingto claim 3 wherein the second comonomer is selected from the groupconsisting of substituted and unsubstituted norbornene, cyclopentadieneand substituted cyclopentadienes, substituted and unsubstituteddicyclopentadienes, cyclohexenes, furans and indenes.
 7. A methodaccording to claim 3 wherein the second comonomer is selected from thegroup consisting of limonene and similar terpenes, vinyl cyclohexanes,vinyl cyclohexenes, vinyl pyridines, vinyl thiophenes, vinylnaphthalenes, vinyl furans, vinyl pyrans and, vinyl pyrrolidones.
 8. Amethod according to claim 3 wherein the second comonomer is an α-olefinhaving an alkyl group selected from the group consisting ofdiisobutylene, isobutylene, n-octene, n-decene, allyglycidylether orvinylisobutylether.
 9. A method according to claim 3 wherein the firstcomonomer is of formula I

wherein R₁ is a metal, quaternary ammonium, phosphonium or sulphoniumcation, R₂ is hydrogen, C₁ to C₄ alkyl or CH₂CO₂H, Y is a carbon atom,the group O═S, or the group POR where R is a hydrogen atom or alkylradical having from 1 to 10 carbon atoms (or carboxylated such radical),R₃ is hydrogen and R₄ is hydrogen, an alkyl radical or a carboxylic acidderivative of formula II

wherein R₅ is OR₆, NR₆R₇ or SR₆, where R₆ and R₇ are hydrogen, alkyl, oralkyl groups with a hetero atom substituent.
 10. A method according toclaim 3 wherein the second comonomer is a vinyl compound of formula III

wherein R₈ represents hydrogen or a straight or branched chain alkyl offrom 1-4 carbon atoms and R₉ represents hydrogen, a branched chain alkylradical of from 1-12 carbon atoms or cycloalkyl radical; and/or thesecond comonomer is a vinyl compound of formula IV

wherein R₁₀ is a straight or branched chain alkyl radical of from 1-4carbons, and R₁₁ is given by formula V, VI or VII

wherein R₁₂ represents one or more alkyl radicals or one or more of H,Cl, OR, SO₃R₁, NO₂ and PO₃R₁, and X is a hetero atom other than carbonwhere R is a hydrogen atom or alkyl radical having from 1 to 10 carbonatoms (or carboxylated such radical) and R₁ is a metal, quaternaryammonium, phosphonium or sulphonium cation; and/or the second comonomeris an olefin of formula VIII

wherein R₁₃ is Cl, SO₃R₁, alkyl, O-alkyl or O-aryl, R₁₄ represents from4-20 carbon atoms such as to make a cyclic or polycyclic alkane orpolyalkenyl compound, and R₁₅ is an epoxide or SO₃R₁ reacted with anunsaturated portion of the ring comprising R₁₄; and/or the secondcomonomer is an exocyclic olefin of formula IX

where R₁₄ and R₁₅ are as hereinabove defined; and/or the secondcomonomer is an internal olefin of formula X,

where R₉ is the same or different and as hereinabove defined.
 11. Amethod according to claim 3 wherein the copolymer contains additionalcomonomer residues which will not substantially change the character ofthe copolymer.
 12. An agricultural formulation comprising at least onefinely divided solid insoluble material and at least one dispersantcomprising a water soluble copolymer wherein said copolymer comprises aresidue of a first comonomer and a residue of a second comonomer,wherein said first comonomer is an α,β-unsaturated oxyacid or anhydrideand said second comonomer is an olefin having at least one polymerizabledouble bond and wherein at least one of said first comonomer and saidsecond comonomer is substituted, wherein the substituents for said firstcomonomer are selected from the group consisting of esters, amides,thioesters and other functional groups derived from reaction withnucleophilic reagents and wherein the substituents for the secondcomonomer are selected from the group consisting of epoxides;sulfonates; esters; amides; and optionally substituted pendent aromaticand heteroaromatic groups wherein said optional substituents areselected from the group consisting of sulfonates, nitrates, phosphatesand other substituents derived from reaction with electrophilicreagents; with the provisos that (a) when the second comonomer issulphonated styrene or sulphonated isobutylene, the first comonomer issubstituted, (b) when one of the first and second comonomers issubstituted with an ester group containing a polyalkyleneoxy moiety, theother of the first and second comonomers must be substituted, (c) whenthe second comonomer is sulphonated styrene, the first comonomer is notalkyl acrylate or alkyl methacrylate, and (d) when the first comonomeris maleic anhydride, the second comonomer is not styrene.
 13. Anagricultural formulation according to claim 12 wherein the formulationis in the form of a suspension concentrate (SC), a wettable powder (WP)or a water dispersible granule (WG).
 14. An agricultural formulationaccording to claim 12 wherein first comonomers are selected from thegroup consisting of fumaric acid, maleic acid and anhydrides, and theesters, amides and imides derived from them, itaconic acid and anhydrideand the corresponding esters amides and imides derived from them,acrylic and methacrylic acids and the esters and amides derived fromthem, vinylphosphonic acid and the corresponding esters and amidesderived from it and ethylene sulphonic acid and the esters and amidesderived from it.
 15. An agricultural formulation according to claim 12wherein the second comonomers are selected from the group consisting ofβ-pinene, 5-ethylidene-2-norbornene, methylene cyclohexane and methylenecyclopentane.
 16. An agricultural formulation according to claim 12wherein the second comonomers are selected from the group consisting ofsubstituted and unsubstituted norbornene, cyclopentadiene andsubstituted cyclopentadienes, substituted and unsubstituteddicyclopentadienes, cyclohexenes, furans and indenes.
 17. Anagricultural formulation according to claim 12 wherein the secondcomonomers are selected from the group consisting of limonene andsimilar terpenes, vinyl cyclohexanes, vinyl cyclohexenes, vinylpyridines, vinyl thiophenes, vinyl naphthalenes, vinyl furans, vinylpyrans and, vinyl pyrrolidones.
 18. An agricultural formulationaccording to claim 12 wherein the olefin is an α-olefin having an alkylgroup selected from the group consisting of diisobutylene, isobutylene,n-octene, n-decene, allylglycidylether and vinylisobutylether.
 19. Anagricultural formulation according to claim 12 wherein the firstcomonomer is of formula I

wherein R₁ is a metal, quaternary ammonium, phosphonium or sulphoniumcation, R₂ is hydrogen, C₁ to C₄ alkyl or CH₂CO₂H, Y is a carbon atom,the group O═S, or the group POR where R is a hydrogen atom or alkylradical having from 1 to 10 carbon atoms (or carboxylated such radical),R₃ is hydrogen and R₄ is hydrogen, an alkyl radical or a carboxylic acidderivative of formula II:

wherein R₅ is OR₆, NR₆R₇ or SR₆, where R₆ and R₇ are hydrogen, alkyl,O-alkyl, or alkyl groups with a hetero atom substituent.
 20. Anagricultural formulation according to claim 12 wherein the secondcomonomer is of formula III

wherein R₈ represents hydrogen or a straight or branched chain alkyl offrom 1-4 carbon atoms, R₉ represents hydrogen, a branched chain alkylradical of from 1-12 carbon atoms, or a cycloalkyl radical; and/or thesecond comonomer is a vinyl compound of formula IV

wherein R₁₀ is a straight or branched chain alkyl radical of from 1-4carbons and R₁₁ is of formula V, VI or VII

wherein R₁₂ represents one or more alkyl radicals or one or more of H,Cl, OR, SO₃R₁, NO₂ and PO₃R₁, and X is a hetero atom other than carbon,where R is a hydrogen atom or alkyl radical having from 1 to 10 carbonatoms (or carboxylated such radical) and R₁ is a metal, quaternaryammonium, phosphonium or sulphonium cation; and/or the second comonomeris an olefin shown by formula VIII,

wherein R₁₃ is Cl, SO₃R₁, alkyl, O-alkyl or O-aryl, R₁₄ represents from4-20 carbon atoms such as to make a cyclic or polycyclic alkane orpolyalkenyl compound and R₁₅ is an epoxide or SO₃R₁ reacted with anunsaturated portion of the ring comprising R₁₄; and/or the secondcomonomer is an exocyclic olefin shown by formula IX

where R₁₄ and R₁₅ are as hereinabove defined; and/or the secondcomonomer is an internal olefin of formula X,

where R₉ is the same or different and as hereinabove defined.
 21. Anagricultural formulation according to claim 12 wherein the copolymercontains additional comonomer residues which will not substantiallychange the character of the copolymer.
 22. An agricultural formulationaccording to claim 12 wherein the dispersant is readily soluble inwater.
 23. An agricultural formulation according to claim 12 wherein thedispersant is an agriculturally acceptable salt of the copolymer andwherein the salt comprises sodium, potassium and/or ammonium ions. 24.An agricultural formulation according to claim 12 wherein the copolymeris polyanionic.
 25. An agricultural formulation according to claim 12wherein the copolymer is in the form of its free acid.
 26. Anagricultural formulation according to claim 12 wherein the dispersant isa water-soluble agriculturally acceptable derivative of the copolymerwherein said derivative is selected from the group consisting ofpolyalkyleneoxy derivatives, polyethyleneglycol derivatives, polyamidederivatives and polyvinyl alcohol derivatives.
 27. An agriculturalformulation according to claim 12 wherein the copolymer has a molecularweight in the range of from 1000 to 90000 daltons.
 28. An agriculturalformulation according to claim 12 wherein the water-insoluble materialsare selected from the group consisting of herbicides, insecticides,fungicides, biocides, molluscicides, algaicides, plant growthregulators, anthelmintics, rodenticides, nematocides, acaricides,amoebicides, protozoacides, fertilizers, crop safeners, fillers andcarriers and other adjuvants.
 29. An agricultural formulation accordingto claim 12 wherein the formulation further comprises a surfactantwetting agent.
 30. An agricultural formulation according to claim 29wherein the surfactant wetting agent is selected from the groupconsisting of an alkylpolysaccharide; di or mono alkyl sulphosuccinatederivative; a nonionic surfactant loaded onto an inert silicate carrier;and a non-ionic surfactant delivered in the form of a urea surfactantcomplex.
 31. A method of making an agrochemical formulation comprisingthe step of: (i) combining at least one finely divided solid insolublematerial, and at least one dispersant comprising a water solublecopolymer wherein said copolymer comprises a residue of a firstcomonomer and a residue of a second comonomer, wherein said firstcomonomer is an α,β-unsaturated oxyacid or anhydride and said secondcomonomer is an olefin having at least one polymerizable double bond andwherein at least one of said first comonomer and said second comonomeris substituted, wherein the substituents for said first comonomer areselected from the group consisting of esters, amides, thioesters andother functional groups derived from reaction with nucleophilic reagentsand wherein the substituents for the second comonomer are selected fromthe group consisting of epoxides; sulfonates; esters; amides; andoptionally substituted pendent aromatic and heteroaromatic groupswherein said optional substituents are selected from the groupconsisting of sulfonates, nitrates, phosphates and other substituentsderived from reaction with electrophilic reagents; with the provisosthat (a) when the second comonomer is sulphonated styrene or sulphonatedisobutylene, the first comonomer is substituted, (b) when one of thefirst and second comonomers is substituted with an ester groupcontaining a polyalkyleneoxy moiety, the other of the first and secondcomonomers must be substituted, (c) when the second comonomer issulphonated styrene, the first comonomer is not alkyl acrylate or alkylmethacrylate, and (d) when the first comonomer is maleic anhydride, thesecond comonomer is not styrene.
 32. A method according to claim 31,further comprising the steps of: (ii) milling said combination to aparticle size range in order to obtain a stable, readily-suspendibleaqueous dispersion; and (iii) stabilising said aqueous dispersion toobtain an SC formulation suitable for dilution in water for agriculturaluse.
 33. A method according to claim 31, further comprising the step of:(ii) milling said combination to a desired particle size to obtain ahomogeneous wettable powder (WP) formulation.
 34. A method according toclaim 31, further comprising the step of: (ii) blending said combinationto obtain a homogeneous wettable powder (WP) formulation.
 35. A methodaccording to claim 31, further comprising the steps of: (ii)agglomerating said combination to form discrete granular materials; and(iii) drying said granular materials to obtain a water dispersiblegranule WG formulation.
 36. A method according to claim 31 wherein thefirst comonomers are selected from the group consisting of fumaric acid,maleic acid and anhydrides, and the esters, amides and imides derivedfrom them, itaconic acid and anhydride and the corresponding estersamides and imides derived from them, acrylic and methacrylic acids andthe corresponding esters and amides derived from them, vinylphosphonicacid and the corresponding esters and amides derived from it andethylene sulphonic acid and the esters and amides derived from it.
 37. Amethod according to claim 31 wherein the second comonomer is selectedfrom the group consisting of β-pinene, 5-ethylidene-2-norbornene,methylene cyclohexane and methylene cyclopentane.
 38. A method accordingto claim 31 wherein the second comonomer is selected from the groupconsisting of substituted and unsubstituted norbornene, cyclopentadieneand substituted cyclopentadienes, substituted and unsubstituteddicyclopentadienes, cyclohexenes, furans and indenes.
 39. A methodaccording to claim 31 wherein the second comonomer is selected from thegroup consisting of limonene and similar terpenes, vinyl cyclohexanes,vinyl cyclohexenes, vinyl pyridines, vinyl thiophenes, vinylnaphthalenes, vinyl furans, vinyl pyrans and vinyl pyrrolidones.
 40. Amethod according to claim 31 wherein the olefin is an α-olefin having analkyl group selected from the group consisting of diisobutylene,isobutylene, n-octene, n-decene, allylglycidylether andvinylisobutylether.
 41. A method according to claim 31 wherein the firstcomonomer is of formula I

wherein R₁ is a metal, quaternary ammonium, phosphonium or sulphoniumcation, R₂ is hydrogen, C₁ to C₄ alkyl or CH₂CO₂H, Y is a carbon atom,the group O═S, or the group POR where R is a hydrogen atom or alkylradical having from 1 to 10 carbon atoms (or carboxylated such radical),R₃ is hydrogen and R₄ is hydrogen, an alkyl radical or a carboxylic acidderivative of formula II

wherein R₅ is OR₆, NR₆R₇ or SR₆, where R₆ and R₇ are hydrogen, alkyl,O-alkyl, or alkyl groups with a hetero atom substituent.
 42. A methodaccording to claim 31 wherein the second comonomer is of formula III

wherein R₈ represents hydrogen or a straight or branched chain alkyl offrom 1-4 carbon atoms, R₉ represents hydrogen, a branched chain alkylradical of from 1-12 carbon atoms, or a cycloalkyl radical; and/or thesecond comonomer is a vinyl compound of formula IV

wherein R₁₀ is a straight or branched chain alkyl radical of from 1-4carbons and R₁₁ is of formula V, VI or VII

wherein R₁₂ represents one or more alkyl radicals or one or more of H,Cl, OR, SO₃R₃, NO₂ and PO₃R₁, and X is a hetero atom other than carbon,where R is a hydrogen atom or alkyl radical having from 1 to 10 carbonatoms (or carboxylated such radical) and R₁ is a metal, quaternaryammonium, phosphonium or sulphonium cation; and/or the second comonomeris an olefin shown by formula VIII

wherein R₁₃ is Cl, SO₃R₁, alkyl, O-alkyl or O-aryl, R₁₄ represents from4-20 carbon atoms such as to make a cyclic or polycyclic alkane orpolyalkenyl compound and R₁₅ is an epoxide or SO₃R₁ reacted with anunsaturated portion of the ring comprising R₁₄; and/or the secondcomonomer is an exocyclic olefin shown by formula IX

where R₁₄ and R₁₅ are as hereinabove defined; and/or the secondcomonomer is an internal olefin of formula X,

where R₉ is the same or different and as hereinabove defined.
 43. Amethod according to claim 31 wherein the copolymer contains additionalcomonomer residues which will not substantially change the character ofthe polymer.
 44. A method according to claim 31 wherein the dispersantis readily soluble in water.
 45. A method according to claim 31 whereinthe dispersant is an agriculturally acceptable salt of the copolymer andwherein the salt comprises sodium, potassium and/or ammonium ions.
 46. Amethod according to claim 31 wherein the copolymer is polyanionic.
 47. Amethod according to claim 31 wherein the copolymer is in the form of itsfree acid.
 48. A method according to claim 31 wherein the dispersant isa water-soluble agriculturally acceptable derivative of the copolymerwherein said derivative is selected from the group consisting ofpolyalkyleneoxy derivatives, polyethyleneglycol derivatives, polyamidederivatives and polyvinyl alcohol derivatives.
 49. A method according toclaim 31 wherein the copolymer has a molecular weight in the range offrom 1000 to 90000 daltons.
 50. A method according to claim 31 whereinthe water-insoluble materials are selected from the group consisting ofherbicides, insecticides, fungicides, biocides, molluscicides,algaicides, plant growth regulators, anthelmintics, rodenticides,nematocides, acaricides, amoebicides, protozoacides, fertilizers, cropsafeners, fillers and carriers and other adjuvants.
 51. An agriculturalformulation produced by the method of any one of claims 31 to 35.